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Physicochemical and Pasting Properties of Cross Linked-Banana Flour

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International Conference on Food Science & Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 292 (2019) 012006 doi:10.1088/1755-1315/292/1/012006

Physicochemical and Pasting Properties of Cross Linked-Banana

Flour

H Marta1*, Y Cahyana2, E Senia2, M Djali1, I R Halim2, S Urrohmah2, D S

Khairunnissa2, A A Sutardi2
1
Laboratory of Food Processing Technology, Food Industrial Technology
Department, Universitas Padjadjaran, Indonesia
2
Laboratory of Food Chemistry, Food Industrial Technology Department, Universitas
Padjadjaran, Indonesia

*Corresponding author (herlina.marta@unpad.ac.id)

Abstract. Role of milieu pH at 5, 8 and 11 has been investigated to determine the

effectiveness of cross-linking by STPP (Sodium tripolyphosphate) to banana flour. Change in
physicochemical and pasting properties due to the treatments have been studied. The
characterization by XRD and FTIR has also been carried out to reveal the diffraction pattern
and the change in the chemical functional group. The result showed that cross-linking at the
pH studied did not change the diffraction pattern of banana flour. An investigation using FTIR
indicated that peak absorbance at wavenumber 2300 and 928 cm-1 increased following the
treatment with the increase of pH, suggesting the formation of diester phosphate and C-O-P
linking respectively. Swelling volume and solubility were remarkably affected by crosslinking
at pH 11 while freeze-thaw stability at pH 5. The effectiveness of cross-linking on changing
the pasting properties was not affected by the pH but cross-linking per se decreased the
breakdown viscosity compared to the native flour.

Keywords: physicochemical properties, pasting properties, cross-linking, banana flour

1. Introduction
Starch is a source of carbohydrate which has an important role in the human diet and also a widely
used component in the food industry. Starch can be produced from several sources such as potato,
sweet potato, corn, rice, wheat, breadfruit, etc. Banana is also a potential starch source, which has a
high amount of starch in unripe banana (more than 60% db) [1]. Native banana starch has some
shortcomings, so it could be modified to improve its properties and application in the food industry.
There are some methods to modify starch i.e. physical, chemical and enzymatic modification, which
gave a different effect on starch characteristics. Some studies have reported about characteristics of
banana starch and flour which affected by cultivar [2], [3], [4] and modification treatments [5], [6].
Cross-linking is one chemical method to modify starch, which used chemical reagents like sodium
trimetaphosphate (STMP), sodium tripolyphosphate (STPP), sodium phosphorous oxychloride,
adipate, and epichlorohydrin. Some previous works have reported that different type of cross-linking
agent affected the physicochemical and pasting properties of starch [7], [8]. Cross-linking of starch
depends on several factors such as starch source, composition and concentration of cross-linking
reagent, reaction time, the extent of substitution, temperature, and pH [9], [10], [11]. Our study
focused on the effect of cross-linking at various pH treatments range of 5-11 on the physicochemical
and pasting properties of banana flour.

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International Conference on Food Science & Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 292 (2019) 012006 doi:10.1088/1755-1315/292/1/012006

2. Materials and Methods

2.1 Materials
Plantain “Nangka” cultivar (genotypes Musa AAB) in a green ripeness state (harvested 8 - 10 weeks
after flowering) were purchased from local market (Gede Bage, Indonesia). Fruit fingers were
selected for uniformity of size, color, and shape. Flour was produced immediately after the purchase
of fresh samples. Chemical reagents were sodium metabisulfite, sodium hydroxide, chloride acid,
sodium sulfate, barium sulfate, and sodium tripolyphosphate. All chemical reagents used in this study
were analytical grade.

2.2 Preparation banana flour and cross-linked banana flour

Banana flour was prepared using method of Cahyana et.al.,[6]. First of all, banana fruit was peeled
and the pulp was then cut into transverse slices approx. 2mm thick. Then the pulp slices were dipped
in water for 10 minutes, drained and dried at 50 °C for 24 hours in a drying oven (Shel Lab). After
that, the pulp slices were milled (Fomac miller machine FCTZ-300) and passed through 80 mesh
screens.
Cross-linked flour with STPP was prepared from banana flour using method of Wu and Seib [12]
with some modification. Banana flour was mixed with water (2:3) to make a mixture and 5% of
Na2SO4 was added. pH value of mixture was adjusted to 5, 8 and 11 by using 0.5 N NaOH or 0.5 N
HCl. Then mixture was heated at 40 °C for 60 minutes with constant stirred using magnetic stirrer and
0.1% STPP was then added. After finishing cross-linking reaction, the mixture was adjusted to pH 6.5
using 0.5 N NaOH or 0.5 N HCl. %. The flour was washed with water 3 times then centrifuged, dried
at 40 C for 24 h and sieved using 80 mesh screens.

2.3 X-ray diffractometer (XRD) and FTIR measurements

Crystalline-type of banana flour was measured using PANalytical X'Pert PRO series PW3040/x0 that
operated using Cu-K alpha radiation with a wavelength of 1.5406 nm as X-ray source at 30 mA and
40 kV. The diffraction angle (2θ) scanning was from 5.0084–49.9734° with a scanning step time of
2.95 seconds. FTIR was used to measure functional group of cross-linked banana starch. Changes in
intensity were measured at a resolution 16 cm-1 in range of 4000-400 cm-1.

2.4 Functional and pasting properties

Water absorption capacity (WAC), swelling volume and solubility, freeze-thawing stability and gel
strength measurement methods refer to (Beuchat,[13] Collado and Corke,[14] Wattanachant et.,
al.[15] and Collado and Corke,[14] , respectively. Rapid Visco Analyzer (RVA StarchMaster 2,
Warriewood, Australia) was used to analyze pasting properties of native and cross-linked banana
flour. Samples and water were mixed to make starch suspension (11% moisture basis) in canister and
then stirred to homogenize the mixture. The starch was equilibrated at 50 °C for 1 minute, then heated
to 95 °C for 3.7 minutes, held at 95 °C for 2.5 minutes, cooled to 50 °C in 3.8 minutes and kept at 50
°C for 2 minutes.

2.5 Statistical analysis

Data were expressed as mean ± SD of triplicate determinations and were compared through one-way
ANOVA using Duncan's Multiple Range test. Statistical significance was set at P < 0.05. Values
followed by the same letter in the comparison were not significantly different (P < 0.05). Statistical
analysis was performed using SPSS version 22.0.

3. Results and Discussion

3.1 Crystalline-Type
XRD diffractogram of native and cross-linked banana flour at various pH was presented in Figure 1.
Native banana flour has a B-type crystalline pattern, which was indicated by a small peak at 5°, strong
peaks at 15 and 17° and a broad peak at 22 - 24° 2θ. Previous work has reported that native banana
starch shown a different type of crystalline pattern such as A-type pattern [16], B-type pattern [2], and
C-type pattern [17]. Similar to native banana flour, all cross-linked banana flour have a B-type
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International Conference on Food Science & Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 292 (2019) 012006 doi:10.1088/1755-1315/292/1/012006

crystalline pattern. It indicated cross-linking at all pH treatment did not alter crystalline-type of
banana starch which in line with [18]. They found that cross-linking did not alter the crystalline type
of kudzu root starch.

Figure 1. XRD diffractograms of native and cross-linked banana

flour at various pH.

3.2 The functional groups

The FTIR (Fourier Transform Infra-Red) test was conducted to determine the functional groups
formed and changed that occurred in the structure of banana flour after the cross-linking treatment.
The functional groups of cross-linked banana flour were at wave number 2930, 2300, 1650, 1159 and
928 cm-1.
Table 1. Effect of pH on functional group of cross-linked banana flour

Area (cm2) Functional

Peak (cm-1)
pH 5 pH 8 pH 11 group
2930 165,346 153,520 141,475 C-H
2300 0,46 5,013 5,315 RO-PO3-R’
1650 36,595 30,742 16,119 C=O
1159 61,110 76,682 122,807 C-O
928 48,21 102,870 127,438 C-O-P

Based on the FTIR spectrum in Table 1, it could be seen at the wave number 1650 cm-1, the higher
pH treatment, the lower area under the curve. Whereas at wave number 2300 cm-1 and 1159 cm-1,
there was an increase in area with increasing pH. The peak of 2300 cm-1 was the phosphate spectrum
which indicated the formation of organic phosphate diester bonds between starch chains (RO-PO3-R')
[19]. The weak peaks around 1200 and 989 cm-1 characterized the existence of C-O-P bonds that
organically cross-linking [20] and peaks ranged 1159-1080 cm-1 characterized C-O bonds. While other
spectra such as carbonyl bonds appeared at 1760-1650 cm-1. According to Chen et at.,[18] the
absorption at 1650 cm-1 was a characteristic absorption band of starch because hydroxyl groups in
water molecules were absorbed by starch which resulted by H2O bending vibration.
Cross-linking decreased the quantity of C-H groups but increased the phosphate spectrum as the
pH value of the solution increased. The reduced quantity of C-H bonds at wave number 2930 cm-1
indicated the presence of a hydrogen group substituted by a phosphate group. The infrared spectrum
peak at wave number 2300 cm-1 increased as the pH increased. The increase in C-O groups indicated
an increase in absorption of water by banana flour, which due to C-O group easily formed C-OH
groups and caused the starch structure to be more amorphous. This increase in C-O group will
increase swelling power, solubility, and water absorption capacity of cross-linked flour, which was in
line with functional properties of cross-linked banana flour in this study. The formation peak at 1650
cm-1 confirmed the presence of carbonyl group (C = O). Increasing pH value caused a decrease in
3
International Conference on Food Science & Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 292 (2019) 012006 doi:10.1088/1755-1315/292/1/012006

carbonyl group in cross-linked banana flour, which due to STPP reagent also attacked the carbonyl
group in the starch granules of banana flour so that the carbonyl group decreased and the phosphate
spectrum increased.

3.3 Functional Properties

Effect of pH on functional properties of cross-linked banana flour was shown in Table 2. Water
absorption capacity (WAC), swelling volume (SV) and solubility (SOL) were remarkably affected by
crosslinking at pH 11 while freeze-thaw stability was affected at all pH treatments. WAC, SV, and
SOL of cross-linked banana flour increased with increasing pH level.

Table 2. Effect of pH on Functional properties of cross-linked banana flour

Treatments
Properties
pH 5 pH 8 pH 11
Water absorption capacity (g/g) 1,913 ± 0,070 a 1,979 ± 0,027 a 2,184 ± 0,038 b
Swelling volume (ml/g) 13,853 ± 0,316 a 14,048 ± 0,414 a 15,861 ± 0,510 b
Solubility (%) 9,163 ± 0,247 a 9,635 ± 0,206 a 12,112 ± 0,120 b
Freeze thaw stability (% syneresis) 0,616 ± 0,053 a 46,624 ± 0,260 c 33,343 ± 0,795 b
Gel strength (gF) 3,247 ± 0,513 a 3,220 ± 0,357 a 3,186 ± 0,700 a
Different letters in the compared values denote significant difference at p < 0.05.

Water absorption capacity (WAC) of cross-linked banana flour ranged from 1.913 – 2.184 g/g db
with the highest WHC at pH 11. The modification of cross-linking in an alkaline condition disrupted
the amorphous region of starch granule which due to the increase in the C-O group. Furthermore,
Karim et.al. [21] suggested that the higher pH modification reduced amylose resistance to expanding
and easy to absorb water. According to Hoover and Sosulki [22], modification of cross-linking
interfered amorphous region of starch and did not change the crystalline pattern of starch.
The increase of WAC at pH 11 also due to intermolecular binding between phosphate and water.
The higher pH, the higher amount of phosphate group which binding with water. This result was
supported by the existence of FTIR spectrum data which showed an increase in absorption peak at
1649.47 cm-1 with increasing pH. Luo et al. [23] have reported that increasing absorption peak around
1646 cm-1 indicated the formation of intermolecular hydrogen bonds H2O in the PO43- group.
Cross-linked banana flour at pH 11 has the highest swelling volume and solubility. The increase in
swelling volume could be due to stronger bonds between starch molecules by phosphate bridges
formed after the cross-linking reaction so that higher the swelling of starch granules [24]. This result
was supported by FTIR data, which showed an increase in the C-O group bond with increasing pH
suspension. The C-O group influenced the swelling of starch granules because easier to form C-OH
groups and causing the starch structure to be more amorphous.
Freeze-thaw stability expressed in percent syneresis can be interpreted as the percentage of the
amount of water that is separated after the paste is treated as a storage at one cycle -15 °C. Cross-
linked banana flour at pH 5 has the lowest syneresis amongst the other samples, approximately 55 and
76 times lower than cross-linked banana flour at pH 8 and 11, respectively. The lower percentage of
separate water shows that the flour gel was more stable to storage at freezing temperatures. Syneresis
generally occurs in starch that has undergone cooling and storage after the gelatinization process. The
low% syneresis in the treatment is in line with the low setback viscosity value.

3.4 Pasting Properties

Pasting properties of cross-linked banana flour were presented in Table 3. The pasting point, peak
viscosity, breakdown and setback of banana flour were not significantly different amongst cross-
linked banana flour samples. It indicated cross-linking at the pH studied did not alter most of pasting
properties. This resulted was in agreement with another previous work [25]. It has found that cross-
linking using POCl3 reagent did not alter peak viscosity of oat starch.
Pasting temperature cross-linked banana flour ranged from 72.68 to 74.02 °C, which was lower
than native banana flour (75.38 °C), which due to cross-linking decreased starch structural stability by
inhibiting double helical bonds such as hydrogen bonds thereby reducing the transfer of heat energy
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International Conference on Food Science & Technology IOP Publishing
IOP Conf. Series: Earth and Environmental Science 292 (2019) 012006 doi:10.1088/1755-1315/292/1/012006

during gelatinization [26]. According to Heo, et al, [27] cross-linked starch required higher energy to
swell due to its process can make starch granule more ordered. They also have found that cross-
linking increased pasting temperature of native potato starch, which was not in line with this study. It
could be due to different starch source and form of samples, which in this study the samples used in
the flour form. Flour form contained higher non-starch components than starch from, which affected
the pasting properties of starch. Peak viscosity of cross-linked banana flour (5190,50 - 5646,50 cP)
higher than native banana flour (5108 cP), which was in agreement with previous works [26], [27],
which due to a new strong covalent bond between starch was occurred during cross-linking treatment.
Cross-linking decreased breakdown of native banana flour. Breakdown viscosity of native and
cross-linked banana flour was 2732.50 cP and 1880.17 – 2184.67 cP, respectively. The lower
breakdown, the higher stability of banana flour to heating and stirring process, which in line with
previous studies [24], [27]. This result indicated that cross-linking prevented loss of viscosity during
heating and stirring process, due to strengthening the swollen granules to breakage under a high
temperature and shear. Setback expressed the ability of starch paste to retrograde, the higher setback
the higher ability of the starch paste to retrograde. Setback viscosity of native banana flour (17.60.50
cP) was in the range of cross-linked banana flour (1536.83 – 2084.83 cP). It indicated cross-linking at
the pH process did not alter setback of native banana flour.

Table 3. Effect of pH on pasting properties of cross-linked banana flour

Properties Treatments
pH 5 pH 8 pH 11
Pasting temperature (°C) 72,68 ± 1,60 a 74,02 ± 0,75 a 73,488 ± 1,21 a
Peak Viscosity (cP) 5190,50 ± 462,90 a 5452,33 ± 355,37 a 5646,50 ± 353,03 a
Hold viscosity (cP) 3112,50 ± 107,847 a 3568,17 ± 94,54 b 3581,50 ± 97,86 b
Final viscosity (cP) 4900,33 ± 163,42 a 5088,33 ± 288,54 a 5788,83 ±221,49 b
Breakdown (cP) 2184,67 ± 296,37 a 1880,17 ± 205,75 a 2065,00 ± 448,62 a
Setback (cP) 1781,17 ± 59,43 a 1536,83 ± 336,34 a 2084,83 ± 317,76 a
Different letters in the compared values denote significant difference at p < 0.05.

4. Conclusion
Cross-linking at all pH treatment did not alter crystalline-type of native banana flour, which has a B-
type crystalline pattern. Peak absorbance at wavenumber 2300 and 928 cm-1 increased following the
increase of pH treatment, suggesting the formation of diester phosphate and C-O-P linking
respectively. Water absorption capacity (WAC), swelling volume (SV) and solubility (SOL) were
remarkably affected by crosslinking at pH 11 while freeze-thaw stability was affected at all pH
treatments. WAC, SV, and SOL of cross-linked banana flour increased with increasing pH level. The
pasting point, peak viscosity, breakdown and setback of banana flour were not significantly different
amongst cross-linked banana flour samples. It indicated cross-linking at the pH studied did not alter
most of pasting properties. Cross-linked banana flour has a higher peak, hold and final viscosity and
lower pasting temperature and breakdown than native banana flour.

Acknowledgments. This research was supported by financial sponsorship from Riset Fundamental
Unpad, Universitas Padjadjaran, Indonesia.

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